CN111511341B

CN111511341B - Colored aqueous particle dispersion comprising at least one particulate dye, a matte effect filler, film-forming polymer particles, a thickener and an ionic polymer dispersant

Info

Publication number: CN111511341B
Application number: CN201880081627.0A
Authority: CN
Inventors: M.埃尔阿赫卡; C.马凯斯-赫利
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 2017-12-20
Filing date: 2018-12-04
Publication date: 2023-10-03
Anticipated expiration: 2038-12-04
Also published as: ES2954363T3; EP3727298C0; FR3075041B1; CN111511341A; WO2019120985A1; US20200390665A1; EP3727298B1; EP3727298A1; FR3075041A1

Abstract

The present invention relates to a composition in the form of an aqueous particle dispersion, comprising in particular a physiologically acceptable medium, in particular for coating keratin materials, more particularly for making up and/or caring for keratin materials such as the skin, comprising: a) An aqueous phase; and b) at least one matte effect filler; and c) solid particles formed from at least one film-forming polymer suspended in the aqueous phase; and d) at least one ionic polymeric dispersant; and e) at least one thickener; and f) at least one particulate dye. The invention also relates to a method for coating keratin materials, more particularly for making up and/or caring for keratin materials such as the skin, characterized in that it comprises the application to the keratin materials of a composition as defined previously.

Description

Colored aqueous particle dispersion comprising at least one particulate dye, a matte effect filler, film-forming polymer particles, a thickener and an ionic polymer dispersant

The present invention relates to the field of care and/or make-up of keratin materials, in particular the skin, and proposes a novel aqueous dispersion of coloured particles which is most particularly advantageous in terms of its technical properties and the feel that it provides to the user when applied to the keratin materials and in particular to the skin.

Cosmetic compositions, such as foundations, are commonly used to impart an aesthetically pleasing color to the skin, but also enhance the aesthetics of irregular skin by making it possible to conceal scarring (marks) and skin pigment anomalies (dyscrasias), reduce the visibility of undulating (relief) imperfections such as pores and wrinkles, and mask blemishes, acne scarring and scars. In this regard, the overlay and matte effect or "soft focus" effect is a desirable primary characteristic.

Emulsions are often attractive to consumers, especially in the context of foundations, because they are easy to apply. For such compositions, it is sought to provide color to enhance the aesthetic appearance of skin. Adequate coverage and matte effects are also sought to hide skin imperfections and to even out skin tone. High proportions of pigments are generally used for this purpose. It is also important that the pigments present in these compositions have good dispersibility in order to obtain stable and homogeneous compositions. In these emulsions, consumers are also looking for products that provide a light texture after application that does not have a thick or heavy effect and that do not transfer to substrates, such as clothing, that come into contact with keratin materials, such as skin. However, emulsions commonly used in make-up have a tendency to have poor performance in terms of freshness and produce a greasy effect due to the presence of large amounts of oil in these emulsions. Furthermore, the lightening effect and/or the transfer resistance effect are not always completely satisfactory.

There remains a need to find novel pigment-based aqueous forms of presentation which are particularly useful as foundations, which have good pigment dispersibility in order to obtain a homogeneous composition, and which give good sensory properties in terms of freshness, non-greasy effect, light texture effect and transfer resistance effect, while at the same time having good cosmetic properties such as good color coverage, good matte effect and good permanence of these effects.

The applicant has surprisingly found that this object can be achieved with a composition in the form of an aqueous particle dispersion, comprising in particular a physiologically acceptable medium, in particular for coating keratin materials, more particularly for making up and/or caring for keratin materials such as the skin, comprising:

a) An aqueous phase; and

b) At least one matte effect filler; and

c) Solid particles formed from at least one film-forming polymer suspended in the aqueous phase; and

d) At least one ionic polymeric dispersant; and

e) At least one thickener; and

f) At least one particulate dye.

This finding forms the basis of the present invention.

Thus, according to one of its aspects, the present invention relates to a composition in the form of an aqueous solid particle dispersion, comprising in particular a physiologically acceptable medium, in particular for coating keratin materials, more particularly for making up and/or caring for keratin materials such as the skin, comprising:

a) An aqueous phase; and

b) At least one matte effect filler; and

d) At least one ionic polymeric dispersant; and

e) At least one thickener; and

f) At least one particulate dye.

The invention also relates to a method for coating keratin materials, more particularly for making up and/or caring for keratin materials such as the skin, characterized in that it comprises the application to the keratin materials of a composition as defined previously.

Definition of the definition

In the context of the present invention, the term "keratin material" means in particular (body, face, or periocular) skin.

The term "physiologically acceptable" means compatible with the skin and/or its covering, having pleasant color, smell and feel and not causing any unacceptable discomfort (stinging or tightening) that tends to prevent the consumer from using such a composition.

The term "aqueous particle dispersion" means any composition comprising an aqueous phase in which particles insoluble in the aqueous phase are dispersed; the composition does not comprise any other phase that is not miscible in the aqueous phase of the composition, regardless of the temperature at which the composition is manufactured.

The term "particles" indicates solid materials that are insoluble in the aqueous phase of the composition, regardless of the temperature at which the composition is manufactured.

The term "filler" should be understood to mean colourless or white, mineral or synthetic particles of any shape which are insoluble and dispersed in the aqueous phase of the composition, whatever the temperature at which the composition is manufactured.

Matte effect or "soft focus" filler

The term matte effect or "soft focus" filler means a filler that imparts a higher transparency and hazy effect to skin tone. The matte effect power of a composition comprising the same can be characterized by the following protocol:

according to the invention, the term "matt effect" means in particular that, after application of the composition according to the invention to the keratin materials, the composition produces a negative gloss value measured using a polarizing camera.

The matte-effect filler used in the composition according to the invention may be in lamellar form (or in platelet form), in spherical form (or in spherical form), in fibrous form, or in any other intermediate form between these defined forms.

In the present patent application, the term "spherical particles" means particles in the shape of spheres or substantially spheres, which are insoluble in the medium of the composition according to the invention even at the melting point of the medium (about 100 ℃).

The term "lamellar particles" means herein particles of parallelepiped shape (rectangular or square surface), disc shape (circular surface) or ellipsoid shape (elliptical surface), characterized by three dimensions: length, width and height, the particles are insoluble in the medium of the composition according to the invention even at the melting point of the medium (about 100 ℃).

The matte-effect filler used in the composition according to the invention is preferably present in a concentration ranging from 0.1% to 5% by weight and more preferably from 1% to 3% by weight relative to the total weight of the composition.

According to a preferred embodiment, the filler is selected from the group comprising: a silica powder; silicone resin powders, in particular polymethylsilsesquioxane powders; polytetrafluoroethylene powder; acrylic copolymer powder; hollow hemispherical silicone particles; hydrophobic silica aerogel particles; a crosslinked elastomeric organopolysiloxane powder; a crosslinked elastomeric organopolysiloxane powder coated with silicone resin; polyamide powder; starch powder; talc/TiO ₂ Alumina/silica composite powder; silica/TiO ₂ A composite material; spherical cellulose particles; clay; perlite; boron nitride and mixtures thereof.

For example, these matte effect fillers may be selected from:

silica powders, e.g. porous Silica particles, e.g. Silica Beads from Sanji Corp (Miyoshi) having an average size of 5 μmAnd Silica Beads->A +.A +.f from Asahi Glass, asahi sub-company>Sunspheres, e.g. Sunspheres of corresponding dimensions 3.5 and 5 μm->Sunsphere/>And Sunsphere->Amorphous silica microspheres coated with polydimethylsiloxane, e.g. under the name SA Sunsphere sold by Asahi Nitsche Corp>And SA Sunsphere->Those sold; by Kobo under the name Silica>Amorphous ellipsoidal hollow silica particles are sold;

polytetrafluoroethylene (PTFE) powder, e.g. Ceridust from Clariant, clariantThose sold;

silicone resin powders, in particular polymethylsilsesquioxane powders, such as those having the following INCI names: polymethylsilsesquioxanes, e.g. by GE Silicone company (GE Silicone) under the name TospearlA product for sale;

acrylic copolymer powder, in particular poly (methyl (meth) acrylate) (PMMA) powder, for example PMMA particles Jurimer from the company Nihon Junyoki with an average size of 8. Mu.mThe name Covabeads by Senxin cosmetic science and technology company (Sensient Cosmetic Technologies) >Hollow PMMA spheres are sold under the trade name Ganzpearl +.>PMMA particles of (b); hollow styrene/acrylate copolymer spheres, e.g. from Romen Hasi Corp (+.>&Haas) under the name SunspheresThose sold; by the name->Expanded vinylidene/acrylonitrile/methylene methacrylate microspheres are sold; hollow spheres of acrylate/ethylhexyl acrylate crosslinked polymer copolymers, e.g.Maquibeads, available from Dadong chemical industry Co., ltd (Daito Kasei Kogyo) under the name Maquibeads->A product for sale; acrylate/ethylhexyl acrylate copolymer microspheres, e.g. from the end product of ponding (Serisu Plastics) under the name TechPolymerThose sold;

hollow hemispherical silicone particles with the INCI name methylsilanol/silicate cross-linked polymer as described in applications JP-2003 128 788 and JP-A-2000-191789, for example NLK from Zhuzu oil Co., ltd (Takemoto Oil and Fat)NLK/>And NLK->

Hydrophobic silica aerogel particles (INCI name: silica silylate), for example by Dow Corning company (Dow Corning) under the name Dow CorningAerogel Fine Particles;

crosslinked elastomeric organopolysiloxane powders, such as Dow Corning 9701Cosmetic from Dow Corning Corp (INCI name: polydimethylsiloxane/vinyl polydimethylsiloxane cross-linked polymer); or by the company Dow Corning under the name EP-9801 Hydronosmetic +.>(INCI name: polydimethylsiloxane/vinyl polydimethylsiloxane cross-linked polymer (and) butylene glycol);

crosslinked elastomeric organopolysiloxane powders coated with silicone resins, in particular silsesquioxane resins, as described for example in patent US 5 538 793. Such elastomer powders are named with the following INCI: vinyl polydimethylsiloxane/polymethylsiloxane silsesquioxane cross-linked polymer and sold by the company Shin-EtsuAnd->Is available; or from Sanjia Kao Co., ltdsei) under the name->Products sold with the INCI name vinyl polydimethylsiloxane/polymethylsiloxane silsesquioxane cross-linked polymer treated with PEG-7 glycerol cocoate, polyquaternium-7 and methylsilanol tri-PEG-8 glycerol cocoate;

polyamidesPowders, e.g.>Nylon 12 particles of the type, e.g. Orgasol 2002EXD NAT from Arkema>And Orgasol 2002UD NAT +.>

Starch powder, in particular aluminum octenyl succinate starch, for example by the company Akzo Nobel under the name Dry Flo A product for sale;

Talc/TiO ₂ Alumina/silica composite powders, e.g. from the Catalyst and chemicals company (Catalyst&Chemicals) under the name CoverleafA product for sale;

silica/TiO ₂ Composite materials such as those sold under the name Sunsil Tin 50 by advanced Chemical company (Sunjin Chemical);

-clays, in particular talc;

spherical cellulose particles, e.g. from Dadong chemical industry Co., ltd. Under the name CellulobeadsThose sold;

-boron nitride;

-perlite;

-and mixtures thereof.

According to a particularly preferred form of the invention, among these matt-effect fillers, those selected from the following will be used:

-a silica powder;

polymethylsilsesquioxane powder with the following INCI name: polymethylsilsesquioxane;

-poly (methyl (meth) acrylate) (PMMA) powder;

-perlite;

-boron nitride;

-and mixtures thereof.

According to a particularly preferred form of the invention, among these matt-effect fillers, those selected from boron nitride, polymethylsilsesquioxane powder and mixtures thereof will be used.

Clay

Among the clays that may be mentioned are the clays of the smectite family (e.g. laponite), the clays of the kaolinite family (e.g. kaolinite, dickite, nacrite), halloysite, du Mbei celeite (dombussite), antigorite, magnetochlorite (berthierine), pyrophyllite, montmorillonite, beidellite, vermiculite, talc, stevensite, hectorite, saponite, chlorite, sepiolite and optionally modified clays of the illite family.

Clays are products which are known per se and are described, for example, in the publication Mine ralogie des argiles [ Clay minerals ], S.caill re, S.H renin, M.Rautureau, 2 nd edition 1982, masson, the teachings of which are incorporated herein by reference.

Natural clays are sedimentary rocks largely composed of certain minerals (usually aluminosilicates). Kaolin is thus a natural clay.

Clays can also be synthetic. Thus, sumecton referred to below is laponite.

Clays can also be chemically modified with different compounds such as acrylic acid, polysaccharides (e.g. carboxymethyl cellulose) or organic cations.

Preferably, in the context of the present invention, a clay is used which is cosmetically compatible and acceptable with the keratin materials. Clays which may be particularly mentioned include kaolinite, montmorillonite, saponite, hectorite and illite. Mixtures of clays and natural clays may also be used.

Natural clays that may be mentioned include green clays, in particular rich in illite; montmorillonite-rich clays, known as fuller's earth, or white clays such as bentonite or otherwise rich in kaolinite. As bentonite, mention may be made in particular of Bentone 38 under the name of Haimassi (Elementis) Bentone Gel CAO/>Bentone 27/>And Bentone Gel MIO->Those sold.

As the montmorillonite-rich clay, there may be mentioned clay known by Rockwood (Rockwood) under the name Gel WhiteAluminum silicate hydrate is sold.

As saponite belonging to the montmorillonite family, mention may be made of laponite, in particular by the name of Kunimine (Kunimine) from the national crest companyAnd (5) selling products.

According to a specific embodiment of the invention, the clay will be talc. The Talc according to the invention may be more particularly selected from the group sold under the name Rose by Nippon Talc companyAnd Talc->Those sold by Luzenac Pharma>A +.o from US Corporation>And Micro +.A Micro sold by Nippon Talc Co., ltd.)>

Perlite

Perlite is a natural glass of volcanic origin, has a glossy black or light gray color, results from rapid cooling of the lava, and is in the form of small particles resembling pearls.

Perlite which can be used according to the invention is typically an aluminosilicate of volcanic origin and has the following composition:

70.0 to 75.0% by weight of silica SiO ₂

12.0 to 15.0 wt.% of alumina Al ₂ O ₃

3.0 to 5.0 percent of sodium oxide Na ₂ O

3.0% -5.0% of potassium oxide K ₂ O

0.5-2% of ferric oxide Fe ₂ O ₃

0.2 to 0.7 percent of magnesium oxide MgO

0.5 to 1.5 percent of calcium oxide CaO

0.05 to 0.15 percent of titanium oxide TiO ₂ 。

Preferably, the perlite particles used in accordance with the invention will be in a porous expanded form.

In a first step, perlite is ground, dried, and then classified by size. The product obtained, called perlite ore, is grey and has a size of about 100 μm. The perlite ore is then expanded (1000 ℃/2 seconds) to produce more or less white particles. When the temperature reaches 850-900 ℃, the water trapped in the structure of the material evaporates and expands the material relative to its original volume. The expanded perlite particles according to the invention can be obtained by the expansion process described in patent US 5 002 698.

Preferably, the perlite particles used are ground; in this case, they are called ground expanded perlite (EMP).

They preferably have a particle size defined by a median diameter D50 in the range from 0.5 to 50 μm and preferably from 0.5 to 40 μm.

Preferably, the perlite particles according to the invention have a particle size distribution such that at least 50% of the particles have a size of less than 20 μm. Furthermore, they preferably have a particle size distribution such that 90% by weight of the particles have a size of less than 55 μm and preferably a size of less than 40 μm. Furthermore, it is preferred that 90% by weight of the particles have a size greater than 5 μm.

Preferably, the perlite particles used have a loose bulk density in the range of 10 to 400kg/m at 25 DEG C ³ (Standard DIN 53468) and preferably from 10 to 300kg/m ³ 。

Will be used in particular under the trade name Optimat 1430 by the company World MineralsAnd OptimatExpanded perlite particles sold, or the commercial products GK-110 +.about.f. sold by the company gallery Xindazhong Filter and Henan Zhongnan Filter Aid>And GK-110 Extra->

Boron nitride

There are several polymorphs of boron nitride: hexagonal boron nitride (denoted as h-BN), rhombohedral boron nitride (denoted as r-BN), amorphous boron nitride (denoted as a-BN), mixed layer boron nitride (denoted as t-BN), cubic boron nitride (denoted as c-BN), and wurtzite type hexagonal boron nitride (denoted as w-BN).

Preferably, the boron nitride particles according to the present invention are selected from mixed layer boron nitride particles, i.e. particles whose crystal planes may be slightly shifted with respect to the theoretical crystal position. The mixed layer boron nitride is a precursor of hexagonal boron nitride (h-BN). It has the same type of characteristics and physical properties as exfoliated hexagonal boron nitride.

Preferably, the particles have an oxygen content ranging from 0.05 to 3 wt%, more preferably from 0.1 to 2.5 wt%, relative to the total weight of the boron nitride particles.

Preferably, the boron nitride particles have an average particle size in the range of 0.1 to 25 μm, preferably 0.3 to 15 μm.

Particle size is measured according to the method of distribution by laser diffraction using Microtrac type from Nikkiso or Mastersizer type equipment from Markov, in particular by measuring the values of D10, D50 and D90.

D10 represents the maximum size of 10% by volume of the particles.

D50 represents the largest dimension that 50% by volume of the particles have.

D90 represents the maximum size of 90% by volume of the particles.

The boron nitride particles may be modified with a surface treatment agent so that amphiphilic properties may be imparted thereon and dispersibility thereof in a composition comprising an oil phase and/or an aqueous phase is promoted.

Alternative treatments include dimethylpolysiloxane (polydimethylsiloxane), linear siloxane polymers terminated with trimethoxysiloxy groups, polymethylhydrosiloxane as a linear polysiloxane known as polymethylsiloxane, and polyoxyalkylene polyalkylether siloxanes such as the polymer PEG-8 methyl ether polydimethylsiloxane.

The boron nitride particles according to the invention may more particularly be selected from the following commercial products:

From caborun corporation (Carborundum)

PUHP from holy Gobi ceramic Co., ltd (Saint Gobain Ceramics)

Boron nitride powder TRES BN PUHP from holy-Gobi ceramic Co

TRES BN PUHP from holy Gobi ceramic Co

From the company holy-gobian(INCI name: boron nitride (and) PEG-8 methyl ether polydimethylsiloxane),

ronaflair Boroneige SF-3 from Merck Co (Merck)

Ronaflair Boroneige from merck corporation

Softouch Boron Nitride from Michaelk Co (Momentive)

Softtouch Boron Nitride CC from mai-image company

Softtouch from michaux corporation

Film-forming polymer particles

The composition according to the invention comprises solid particles formed of one or more film-forming polymers suspended in the aqueous phase of the composition.

The solid film-forming polymer particles may be used as such and suspended in the aqueous phase of the composition, or may be used in the form of particles in an aqueous dispersion (latex or pseudolatex).

In the present patent application, the term "film-forming polymer" means a polymer capable of forming a continuous film on a support, either by itself or in the presence of an auxiliary film-forming agent, at a temperature ranging from 20 ℃ to 150 ℃.

Such film-forming polymers present in the form of particles in aqueous dispersions are generally referred to as (pseudo) latices, i.e. latices or pseudo latices. Techniques for preparing these dispersions are well known to those skilled in the art.

The composition according to the invention may comprise one or more types of particles, which may differ in terms of their size, their structure and/or their chemical nature.

The film-forming polymer is preferably present at a solids content ranging from 0.1 wt% to 5 wt%, more preferably ranging from 0.1 wt% to 3 wt%, even more preferably ranging from 0.1 wt% to 2 wt%, and more particularly from 0.1 wt% to 1.5 wt% relative to the total weight of the composition.

These solid particles may have anionic, cationic or neutral properties and may constitute a mixture of solid particles having different properties.

In the present invention, the term "aqueous" refers to a liquid medium based on water and/or hydrophilic solvents. The aqueous liquid medium may consist essentially of water. It may also comprise a mixture of water and one or more organic solvents miscible with water (the miscibility with water being greater than 50% by weight at 25 ℃) such as lower monohydric alcohols containing from 1 to 5 carbon atoms, such as ethanol or isopropanol, glycols containing from 2 to 8 carbon atoms, such as propylene glycol, ethylene glycol, 1, 3-butanediol and dipropylene glycol, C ₃ -C ₄ Ketones and C ₂ -C ₄ Aldehydes.

Among the film-forming polymers which can be used in the compositions of the invention, mention may be made of synthetic polymers of the radical type or of the polycondensate type and polymers of natural origin and mixtures thereof. Typically, these polymers may be statistical polymers, multi-block copolymers of type A-B, A-B-A or ABCD, or even graft polymers.

Free radical film forming polymers

The term "radical polymer" means a polymer obtained by polymerization of unsaturated monomers and in particular olefinic monomers, each monomer being capable of homopolymerization (unlike polycondensates).

The free radical film-forming polymer may be in particular an acrylic and/or vinyl homo-or copolymer.

The vinyl film-forming polymer may result from the polymerization of ethylenically unsaturated monomers containing at least one acid group and/or esters of these acid monomers and/or amides of these acid monomers.

Ethylenically unsaturated monomers containing at least one acid group or monomers bearing an acid group that may be used include alpha, beta-ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid or itaconic acid. (meth) acrylic acid and crotonic acid are particularly used, and (meth) acrylic acid is more particularly used.

The esters of acid monomers are advantageously chosen from (meth) acrylic esters (also known as (meth) acrylic esters), in particular alkyl groups, in particular C ₁ -C ₂₀ And more particularly C ₁ -C ₈ Alkyl (meth) acrylates; aryl, especially C ₆ -C ₁₀ Aryl (meth) acrylates; hydroxyalkyl radicals, especially C ₂ -C ₆ (meth) acrylic esters of hydroxyalkyl groups; and allyl methacrylate.

Among the alkyl (meth) acrylates that may be mentioned are methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate and lauryl methacrylate.

Among the hydroxyalkyl (meth) acrylates, mention may be made of hydroxyethyl acrylate, 2-hydroxypropyl acrylate, hydroxyethyl methacrylate or 2-hydroxypropyl methacrylate.

Among the aryl (meth) acrylates, mention may be made of benzyl acrylate and phenyl acrylate.

(meth) acrylic esters are in particular alkyl (meth) acrylates and allyl methacrylates.

According to the invention, the alkyl groups of the esters may be fluorinated or perfluorinated, i.e. some or all of the hydrogen atoms of the alkyl groups are replaced by fluorine atoms.

Examples of amides of acid monomers which may be mentioned are (meth) acrylamides, and in particular N-alkyl (meth) acrylamides, in particular C ₂ -C ₁₂ N-alkyl (meth) acrylamides of alkyl groups. Among the N-alkyl (meth) acrylamides that may be mentioned are N-ethylacrylamide, N-tert-butylacrylamide and N-tert-octylacrylamide.

Vinyl film-forming polymers may also be produced by homo-or co-polymerization of monomers selected from vinyl esters and styrene monomers. In particular, these monomers may be polymerized with acid monomers and/or esters thereof and/or amides thereof, such as those mentioned above.

Examples of vinyl esters which may be mentioned are vinyl acetate, vinyl neodecanoate, vinyl pivalate, vinyl benzoate and vinyl tert-butylbenzoate.

Styrene monomers which may be mentioned include styrene and alpha-methylstyrene.

The list of monomers given is not limiting and any of the monomers known to those skilled in the art to be included in the classes of acrylic and vinyl monomers (including monomers modified with silicone chains) may be used.

Vinyl polymers that may also be used include silicone acrylic polymers.

Mention may also be made of polymers resulting from the radical polymerization of one or more radical monomers inside and/or partially on the surface of particles of at least one pre-existing polymer selected from the group consisting of polychloroethyl, polyurea, polyester, polyesteramide and/or alkyd resins. These polymers are commonly referred to as "hybrid polymers".

Polycondensates

As film-forming polymers of the polycondensate type, mention may be made of anionic, cationic, nonionic or amphoteric polychloroethers, acrylic polychloroethers, polyvinylpyrrolidone-polychloroethers, polyester-polychloroethers, polyether-polychloroethers, polyureas, polyurea/polychloroethers and silicone polychloroethers, and mixtures thereof.

The film-forming polychloroethyl ester can be, for example, an aliphatic, cycloaliphatic or aromatic polychloroethyl ester, polyurea/urethane or polyurea copolymer comprising, alone or as a mixture, at least one block selected from the group consisting of:

-blocks of aliphatic and/or cycloaliphatic and/or aromatic polyester origin, and/or

Branched or unbranched silicone blocks, for example polydimethylsiloxane or polymethylphenylsiloxane, and/or

-a block comprising fluoro groups.

Film-forming polychlorinated esters as defined in the present invention may also be obtained from branched or unbranched polyesters or from alkyd resins containing labile hydrogens modified by reaction with diisocyanates and difunctional organic compounds, such as dihydro, diamino or hydroxyamino groups, and also containing carboxylic acid or carboxylic acid ester groups, or sulfonic acid ester groups, or alternatively neutralizable tertiary or quaternary amine groups.

Among the film-forming polycondensates, mention may also be made of polyesters, polyesteramides, aliphatic polyesters, polyamides and epoxy ester resins.

The polyesters can be obtained in a known manner by polycondensation of dicarboxylic acids with polyols, in particular diols.

The dicarboxylic acids may be aliphatic, cycloaliphatic or aromatic. Examples of such acids that may be mentioned include: oxalic acid, malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, 2-dimethylglutaric acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, maleic acid, itaconic acid, phthalic acid, dodecanedioic acid, 1, 3-cyclohexanedicarboxylic acid, 1, 4-cyclohexanedicarboxylic acid, isophthalic acid, terephthalic acid, 2, 5-norbornanedicarboxylic acid, diglycolic acid, thiodipropionic acid, 2, 5-naphthalenedicarboxylic acid, 2, 6-naphthalenedicarboxylic acid. These dicarboxylic acid monomers may be used alone or as a combination of at least two dicarboxylic acid monomers. Among these monomers, particularly selected monomers are phthalic acid, isophthalic acid and terephthalic acid.

The diol may be selected from aliphatic, cycloaliphatic and aromatic diols. The diols used are chosen in particular from: ethylene glycol, diethylene glycol, triethylene glycol, 1, 3-propanediol, cyclohexanedimethanol and 4-butanediol. Other polyols that may be used are glycerol, pentaerythritol, sorbitol and trimethylolpropane.

The polyesteramides can be obtained in a manner analogous to polyesters by polycondensation of diacids with diamines or aminoalcohols. Diamines which may be used are ethylenediamine, hexamethylenediamine and m-phenylenediamine or p-phenylenediamine. An amino alcohol which may be used is monoethanolamine.

Optionally modified polymers of natural origin, such as shellac resins, mountain gums, dammar resins, elemene, copa resins, water insoluble cellulose-based polymers such as nitrocellulose, modified cellulose esters (including especially carboxyalkyl cellulose esters, such as those described in patent application US 2003/185 774), and mixtures thereof, may be used in the present invention.

According to a specific embodiment of the present invention, the at least one film-forming polymer in the dispersed state is selected from the group consisting of acrylic polymer dispersions, polychloroethyl ester dispersions, sulfopolyester dispersions, vinyl dispersions, polyvinyl acetate dispersions, vinyl pyrrolidone, dimethylaminopropyl methacrylamide and lauryl dimethylaminopropyl methacrylamide ammonium chloride terpolymer dispersions, polychloroethyl ester/polyacrylic hybrid polymer dispersions and core-shell particle dispersions, and mixtures thereof.

Various types of aqueous dispersions, particularly commercial aqueous dispersions, suitable for preparing the compositions according to the invention are detailed below.

1/thus, according to a preferred embodiment of the invention, the aqueous dispersion of polymer particles is an aqueous dispersion of acrylic polymer.

The acrylic polymer may be a styrene/acrylate copolymer and is in particular selected from the group consisting of at least one styrene monomer and at least one (meth) acrylic acid C ₁ -C ₁₈ Polymers of copolymers produced by polymerization of alkyl ester monomers. As the styrene monomer that can be used in the present invention, examples that may be mentioned include styrene and α -methylstyrene, and in particular styrene.

(meth) acrylic acid C ₁ -C ₁₈ Alkyl ester monomers, in particular C (meth) acrylic acid ₁ -C ₁₂ Alkyl esters and more particularly C (meth) acrylic acid ₁ -C ₁₀ Alkyl esters. (meth) acrylic acid C ₁ -C ₁₈ The alkyl ester monomer may be selected from methyl acrylate, methyl methacrylate, ethyl acrylate, propyl acrylate, butyl methacrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate.

As acrylic polymers in aqueous dispersion, according to the invention, use can be made of Joncryl, by the company Basoff Styrene/acrylate copolymers sold under the index number by the company basfAcrylic polymers sold by DS-6250 or acrylic copolymers sold by Basv company95。

As acrylic polymer in aqueous dispersion, according to the invention, an aqueous dispersion of an amino methylpropanolate of a copolymer of allyl methacrylate with one or more monomers selected from acrylic acid, methacrylic acid or esters thereof, having the following INCI name, will be used more particularly: acrylic/methacrylic copolymer AMP salts, for example, lu Bo Fixate G-100L PR, a commercial product in the form of a 25% to 28% by weight aqueous dispersion from Advance materials Co., ltd (Lubrizol Advanced Materials, inc.)

According to one embodiment variant of the invention, the aqueous dispersion of polymer particles is an aqueous dispersion of polyester-polychloroethyl and/or polyether-polychloroethyl particles, in particular in anionic form.

The anionic nature of the polyester-and polyether-polychloroetsters used according to the invention is due to the presence of groups bearing carboxylic or sulphonic acid functions in their constituent units.

The polyester-polychloroethyl or polyether-polychloroethyl particles used according to the present invention are generally sold in the form of aqueous dispersions.

The particle content of the dispersions currently available on the market ranges from about 20% to about 50% by weight relative to the total weight of the dispersion.

Among the anionic polyester-polychloroethyl ester dispersions which can be used in the aqueous varnish according to the invention, mention may in particular be made of the one known by the name avaure UR by the company Noveon (Noveon)And (5) selling products.

Can be used according to the inventionAmong the anionic polyether-polychloroethyl particle dispersions, mention may be made in particular of the names Avalure UR by the company nuxAnd Neorez R +.A by Dissman Co., ltd (DSM) under the name Neorez R->And (5) selling products.

According to a specific embodiment of the invention, a mixture of commercial dispersions consisting of anionic polyester-polychloroethyl particles as defined above and anionic polyether-polychloroethyl particles also defined above can be used.

For example, the product of Sancure under the name Sancure may be usedMixtures of dispersions sold or under the name Avalure UR->Products sold and under the name Avalure UR->Mixtures of products are sold, these dispersions being sold by the reputation company.

According to another embodiment of the invention, the aqueous dispersion used comprises a mixture of at least two film-forming polymers in the form of solid particles, said film-forming polymers differing in their respective glass transition temperatures (Tg).

In particular, according to one embodiment of the present invention, the composition according to the present invention may comprise at least one first film-forming polymer in a dispersed state and at least one second film-forming polymer in a dispersed state, the first and second polymers having different Tg values, and preferably the first polymer (Tg ₁ ) Higher than the (Tg) of the second polymer ₂ ). In particular, tg ₁ And Tg of ₂ The difference between the values being at least as absolute value10 ℃, and preferably at least 20 ℃.

More precisely, the composition comprises, in an acceptable aqueous medium:

-solid particles of a first film-forming polymer dispersed in an aqueous medium, said first film-forming polymer having at least one glass transition temperature Tg of 20 ℃ or higher ₁ A kind of electronic device

-solid particles of a second film-forming polymer dispersed in an aqueous medium, said second film-forming polymer having at least one glass transition temperature Tg2 of less than or equal to 70 ℃.

This dispersion is typically produced by mixing an aqueous dispersion of two film-forming polymers.

The first film-forming polymer has at least one, and in particular has a glass transition temperature Tg of greater than or equal to 20deg.C, in particular in the range from 20deg.C to 150deg.C, and advantageously greater than or equal to 40deg.C, in particular in the range from 40deg.C to 150deg.C, and in particular greater than or equal to 50deg.C, in particular in the range from 50deg.C to 150deg.C ₁ 。

The second film-forming polymer has at least one, and in particular has a glass transition temperature Tg of less than or equal to 70 ℃, in particular in the range of from-120 ℃ to +70 ℃, in particular less than 50 ℃, in particular in the range of from-60 ℃ to +50 ℃, and more in particular in the range of from-30 ℃ to +30 DEG C ₂ 。

The measurement of the glass transition temperature (Tg) of the polymer was performed by DMTA (dynamic and mechanical temperature analysis), as described below.

To measure the glass transition temperature (Tg) of the polymer, a viscoelastic test was performed on the film samples using a polymer laboratory (Polymer Laboratories) DMTA machine. The film was prepared by pouring an aqueous dispersion of the film-forming polymer into a teflon coated substrate, followed by drying at 120 ℃ for 24 hours. A film is then obtained from which the sample is cut (e.g., using a punch). These samples are typically about 150 μm thick, 5 to 10mm wide, and have a useful length of about 10 to 15 mm. Tensile stress was applied to this sample. The sample was subjected to a static force of 0.01N, on which a sinusoidal displacement of + -8 μm at a frequency of 1Hz was superimposed. Thus, the test is performed in the linear range at low deformation levels. This tensile stress was applied to the sample at a temperature ranging from-150 ℃ to +200 ℃, with a temperature change of 3 ℃/min.

The complex modulus of the tested polymers was then measured as a function of temperature e=e' +ie.

From these measurements, the dynamic moduli E' and E "and the damping power were derived: tgδ=e "/E'.

Then drawing a curve of tg delta values as a function of temperature; this curve exhibits at least one peak. The glass transition temperature Tg of the polymer corresponds to the temperature at the top of this peak.

When the curve has at least two peaks (in which case the polymer has at least two Tg values), the value of Tg considered for the test polymer is the temperature at which the curve has the peak of maximum amplitude (i.e., corresponding to the maximum Tg delta value; in which case only the "major" Tg is considered to be the Tg value for the test polymer).

In the present invention, when the first film-forming polymer has at least two Tg values, the transition temperature Tg ₁ A "major" Tg (in a predetermined sense) corresponding to the first film-forming polymer; when the second film-forming polymer has at least two Tg values, the glass transition temperature Tg ₂ Corresponds to the "major" Tg of the second film-forming polymer.

The first film-forming polymer and the second film-forming polymer may be selected, independently of each other, from the group consisting of radical polymers, polycondensates and polymers of natural origin as previously defined having the previously defined glass transition temperature characteristics.

As the first film-forming polymer in the aqueous dispersion, use may be made of a polymer known by the name Neorez from Dissman CorpJoncryl +.A. By Basoff company under the name Joncryl->And Joncryl->Aqueous polymer dispersions are sold.

As the second film-forming polymer in the aqueous dispersion, for example, a film-forming polymer known by the name Avalure by Noyu corporation can be usedAnd Avaluure->Aqueous polymer dispersions sold or under the name Acrilem by ICAP companyAqueous polymer dispersions sold and Neocryl +.A.A.of the Dissman company>Aqueous polymer dispersions are sold.

Aqueous dispersion avaureIs a polychloroethyl ester obtained by polycondensation of polytetramethylene oxide, tetramethylxylylene diisocyanate, isophorone diisocyanate and dimethylolpropionic acid.

According to one embodiment of the invention, a styrene/acrylate polymer dispersion is used, such as Joncryl, which is available from Basoff Inc. under the index numberDispersion and acrylic polymer dispersions are sold, for example, by Dissman under the index Neocryl->The combination of the dispersions sold is used as the first and second film-forming polymers in the aqueous dispersion.

According to another embodiment of this embodiment of the invention above 3/Point With acrylic polymer dispersions, e.g. Joncryl by Basoff company under the indexThe dispersion sold as the first film-forming polymer in aqueous dispersion and was prepared using the index Avalure by Dissman>Anionic polychloroethyl polymer dispersions are sold as the second film-forming polymer.

4/according to yet another embodiment of the invention, the composition comprises at least one specific multiphase aqueous dispersion.

More specifically, it comprises, in an acceptable aqueous medium, a dispersion of particles comprising at least one at least partially external flexible phase comprising at least one polymer having at least one glass transition temperature Tg and at least one at least partially internal rigid phase ₂ The rigid phase being a polymer having at least one glass transition temperature Tg ₁ Is amorphous, tg ₁ Above Tg ₂ The flexible polymer is at least partially attached to the rigid phase by chemical grafting.

In particular, tg ₁ And Tg of ₂ The difference between the values is as absolute value at least 10 ℃, and preferably at least 20 ℃.

Particles according to the invention, also referred to as multiphase (or composite) particles, are particles comprising at least one flexible phase and at least one rigid phase.

The flexible polymer of the particles in the dispersion may have at least one glass transition temperature of less than or equal to 70 ℃, in particular in the range of-120 ℃ to 70 ℃, more particularly less than or equal to 30 ℃, in particular in the range of-60 ℃ to 30 ℃.

The flexible polymer may be selected from block and/or random polymers. The term "block and/or random polymer" means a polymer in which the distribution of monomers on the main or side chain units is in block and/or random form.

The flexible polymer may be selected from the group consisting of radical polymers, condensation polymers and silicone polymers. The flexible polymer may be selected from the group consisting of polyacrylic, polymethacrylic, polyamide, polychloroethyl, polyolefin (especially polyisoprene, polybutadiene, polyisobutylene (PIB)), polyester, polyvinyl ether, polyvinylsulfide, polyoxide, polysiloxane, and especially Polydimethylsiloxane (PDMS), and combinations thereof. The term "combination" means a copolymer that can be formed from monomers that result in the formation of the polymer.

In particular, the flexible polymer may be selected from poly (meth) acrylic, polychloroethyl, polyolefin and polysiloxane.

The amorphous material of the rigid phase has a glass transition temperature of greater than 20 ℃, in particular in the range of 20 ℃ to 150 ℃, in particular greater than or equal to 30 ℃, in particular in the range of 30 ℃ to 150 ℃, preferably greater than or equal to 40 ℃, more in particular in the range of 40 ℃ to 150 ℃, or even greater than or equal to 50 ℃, in particular in the range of 50 ℃ to 150 ℃.

The amorphous material of the rigid phase may be a polymer, especially a block and/or random polymer. It may be a polymer selected from the group consisting of: polyacrylic acids, polymethacrylic acids such as poly (meth) acrylic acid, poly (meth) acrylamide, polyvinyl compounds, polyvinyl esters, polyolefins, polystyrene, polyvinyl halides such as polyvinyl chloride (PVC), polyvinyl nitrile, polychloroethyl esters, polyesters, polyamides, polycarbonates, polysulfones, polysulfonamides, polycyclic species having a carbocyclic ring in the backbone such as polyphenylene or polyoxyphenylene, and combinations thereof.

Advantageously, the amorphous material of the rigid phase may be a polymer selected from: polyacrylic, polymethacrylic, such as poly (meth) acrylic acid, poly (meth) acrylamide, polyvinyl compounds, polyvinyl esters, polyolefins, polystyrene, polyvinyl halides, such as polyvinyl chloride (PVC), polyvinyl nitrile, polychloroethyl, polyamides, and polyesters.

According to a particular embodiment of the invention, the flexible phase and the rigid phase of the multiphase particle may comprise at least one free radical polymer obtained by or even substantially by polymerization of a monomer selected from the group consisting of:

- (meth) acrylic esters, e.g. alkyl (meth) acrylates, especially with C ₁ -C ₈ Alkyl (meth) acrylate esters of alkyl groups,

vinyl esters of straight-chain or branched carboxylic acids, such as vinyl acetate or vinyl stearate,

styrene and its derivatives, such as chloromethylstyrene and alpha-methylstyrene,

conjugated dienes, such as butadiene or isoprene,

acrylamide, methacrylamide and acrylonitrile,

vinyl chloride, and

- (meth) acrylic acid.

The choice (nature and amount) of monomers, which may be a single monomer or a mixture of at least two monomers, of the flexible polymer and the amorphous material of the rigid phase is determined by the glass transition temperature desired to be imparted to each polymer.

The polymers of the rigid and/or flexible phase may be crosslinked by means of monomers bearing at least two copolymerizable double bonds, for example selected from:

conjugated dienes, such as butadiene or isoprene,

allyl esters of alpha, beta-unsaturated carboxylic acids, such as allyl acrylate or allyl methacrylate,

allyl esters of alpha, beta-unsaturated dicarboxylic acids, such as diallyl maleate,

polyacrylic or polymethacrylic acids generally comprising at least two ethylenic unsaturations, such as ethylene glycol dimethacrylate, 1, 3-butanediol dimethacrylate, 1, 4-butanediol diacrylate or pentaerythritol tetraacrylate;

Polyethylene compounds, such as divinylbenzene or trivinylbenzene, and

polyallyl compounds, such as triallyl cyanurate.

Chemical grafting allows the rigid and flexible phases of the multiphase particles to be stably bonded by forming covalent bonds.

Chemical grafting can be carried out by block radical polymerization (also known as sequential polymerization) according to procedures well known to those skilled in the art. The block polymerization comprises polymerizing the monomers of the rigid polymer (polymer forming the particulate rigid phase) in a first step and then continuing to polymerize with the monomers of the flexible polymer (polymer forming the particulate flexible phase) in a second step. In this way, the polymer chains of the flexible phase are at least partially bonded to the polymer chains of the rigid phase by covalent bonds resulting from the polymerization of the monomers of the flexible polymer with the monomers of the rigid polymer.

Advantageously, the monomers of the polymer of the outer flexible phase have a greater affinity for the dispersion medium than the monomers of the polymer of the inner rigid phase.

The flexible polymer may be grafted onto the rigid polymer by a grafting monomer, which may be a monomer with several double bonds (ethylenic bonds), in particular a monomer with two ethylenic double bonds. The grafting monomers may be conjugated dienes such as those described previously, or allyl esters (especially diesters) of α, β -unsaturated dicarboxylic acids such as those described previously (e.g., diallyl maleate) with two polymerizable functional groups (olefinic double bonds) having different reactivities: one of the polymerizable functional groups of the grafting monomer (olefinic double bond) is polymerized with the polymer of the amorphous material of the rigid phase (rigid polymer) and the other polymerizable functional group of the same grafting monomer (olefinic double bond) is polymerized with the flexible polymer.

When the flexible polymer or the polymer of the rigid phase is a polycondensate, a polycondensate with at least one ethylenic unsaturation is particularly used which is capable of reacting with monomers which also comprise ethylenic unsaturation to form covalent bonds with the polycondensate. Polycondensates containing one or more ethylenic unsaturations are obtained, in particular, by polycondensation of monomers such as allyl alcohol, vinylamine or fumaric acid. For example, a vinyl monomer may be polymerized with a polychloroethyl ester having a vinyl group in the polychloroethyl ester chain or at the end of the polychloroethyl ester chain, and thus the vinyl polymer grafted onto the polychloroethyl ester; particle dispersions of such grafted polymers are described in particular in publications The structure and properties of acrylic-polyurethane hybrid emulsions [ structure and properties of acrylic-polychloroethyl hybrid emulsions ], hiroze m., progress in Organic Coatings [ progress of organic coatings ],38 (2000), pages 27-34; survey of the applications, properties, and technology of crosslinking emulsions [ application, properties and technical overview of crosslinked emulsions ], bufkin b., journal of Coatings Technology [ journal of coating technology ], volume 50, 647, 1978, month 12.

The same grafting principle applies to silicones using silicones comprising vinyl groups, so that vinyl monomers can be polymerized on the silicone and thus vinyl polymer chains grafted onto the silicone.

The particles with rigid and flexible phases generally have a size in the range of 1nm to 1 μm, and in particular in the range of 10nm to 1 μm.

The flexible phase may be present in the particles in an amount of at least 1% by volume, in particular at least 5% by volume, in particular at least 10% by volume, and more in particular at least 25% by volume, relative to the total volume of the particles. The flexible phase may be present in the particles in a content ranging up to 99.999% by volume, in particular up to 99.9% by volume, in particular up to 99% by volume, and more in particular up to 95% by volume. In particular, the flexible phase may be present in the particles in a content ranging from 1% to 99.999% by volume, in particular ranging from 5% to 99.9% by volume, more in particular ranging from 10% to 99.9% by volume, in particular ranging from 25% to 99.9% by volume, more in particular ranging from 50% to 95% by volume, or even ranging from 50% to 90% by volume.

In all cases, the rigid phase and the flexible phase are incompatible, i.e. they can be distinguished by using techniques well known to the person skilled in the art, for example by techniques of electron microscopy or by techniques of measuring the glass transition temperature of the particles by differential calorimetry. Thus, the multiphase particles are heterogeneous particles.

The morphology of the flexible and rigid phases of the dispersed particles may be, for example, core-shell with the shell particles completely surrounding the core, but may also be core-shell with multiple cores, or an interpenetrating network of phases. In the multiphase particles, the flexible phase is at least partially and in particular mainly external and the rigid phase is at least partially and in particular mainly internal.

Heterogeneous particles can be prepared from different types of monomers by a continuous series of polymerizations. The particles of the first monomer family are typically prepared in a separate step or formed in situ by polymerization. Next, or simultaneously, other families of at least one other monomer are polymerized in at least one additional polymerization step. The particles so formed have at least one structure or core structure that is at least partially internal and at least one structure or shell structure that is at least partially external. Thus, a "multi-layer" heterostructure can be formed. From which various forms of core-shell type can be obtained, but also for example fragments of rigid phase can be entrained in the flexible phase. According to the invention, it is important that at least part of the outer flexible phase structure is more flexible than at least part of the inner rigid phase structure.

According to a specific embodiment of the invention, the multiphase particles may be dispersed in an aqueous medium, in particular a hydrophilic medium. The aqueous medium may consist essentially of water, and in particular almost entirely of water. These dispersed particles thus form an aqueous polymer dispersion, which is commonly referred to as a latex or pseudolatex. The term "latex" means an aqueous dispersion of polymer particles, such as may be obtained by emulsion polymerization of at least one monomer.

The heterogeneous particle dispersions are generally prepared via at least one emulsion polymerization in a substantially aqueous continuous phase using a reaction initiator for free radical polymerization, such as a photochemical or thermal initiator, optionally in the presence of additives such as stabilizers, chain transfer agents and/or catalysts.

As solid particles of the film-forming polymer according to the invention, it is possible to more preferably use:

aqueous dispersions of acrylic polymers, e.g. known by the name Acronal from basfThose sold under the name Neocryl by Dissman>Neocryl/>NeocrylNeocryl/>Neocryl/>Neocryl/>And NeocrylThose sold under the name Joncryl by Basoff company>And Joncryl->Those sold under the name Daitosol 5000 +. >(INCI name: acrylic acid (ester) based copolymer) or Daitosol 5000 +.>(INCI name: acrylic acid (ester)/ethylhexyl acrylate copolymers; synthran ++by Thai Polymer Co (Interpoler) under the name Synthran->(INCI name: styrene/acrylic acid (ester) based/ammonium methacrylate copolymers) those sold, aqueous dispersions of aminomethyl propanoates of copolymers of allyl methacrylate and one or more monomers selected from acrylic acid, methacrylic acid or esters thereof, having the following INCI name: acrylic acid ester/allyl methacrylate copolymer AMP salts, for example, lu Bo Fixate G-100L PR->

By Dissman under the name NeorezAnd Neorez>Aqueous polychloroethyl dispersions are sold under the name Avalure>Avalure/>Avalure/>Avalure/>Sancure/>Avalure/>And Avaluure UR->Aqueous polymers for saleChloro ester dispersion, and the name Impranil>The aqueous polychloroethyl ester dispersions which are sold,

sulfopolyester dispersions, for example Eastman, under the trade name Eastman, by the company Isman chemical products (Eastman Chemical Products)Those that are sold are offered for sale,

vinyl dispersions, e.g. Mexomer Aqueous dispersions of polyvinyl acetate, for example from Nisshin Chemical, inc>Or products sold by Union Carbide, aqueous dispersions of terpolymers of vinylpyrrolidone, dimethylaminopropyl methacrylamide and lauryl dimethylaminopropyl methacrylamide chloride such as Styleze from ISP>

Aqueous dispersions of polychloroethyl/polyacrylic hybrid polymers, e.g. from Air Products (Air Products) with index numbersProducts sold or from National Starch company (National Starch)

Aqueous dispersions of core-shell particles, e.g. of the type indicated by the index number by the company ArkemaProducts sold (core: fluorinated-shell: acrylic) or alternatively those described in US 5 188 899 (core: silica-shell: silicone) and mixtures thereof.

According to a particularly preferred form of the invention, an aqueous dispersion of an amino methyl propanoate salt of a copolymer of allyl methacrylate with one or more monomers selected from acrylic acid, methacrylic acid or esters thereof, having the following INCI name, will be used: acrylic/methacrylic copolymer AMP salts, e.g. Lu Bo Fixate G-100L PR, a commercial product in the form of a 25% to 28% by weight aqueous dispersion from Advance materials Co., ltd )。

Ionic polymeric dispersants

The ionic polymeric dispersant is preferably selected from:

- (meth) acrylic acid homopolymer and salts thereof,

- (meth) acrylic acid copolymer and its salt,

styrene/(meth) acrylic acid copolymers and salts thereof,

vinyl naphthalene/(meth) acrylic acid copolymer and its salt,

styrene/maleic acid copolymers and salts thereof,

vinyl naphthalene/maleic acid copolymer and salts thereof,

maleic anhydride copolymers and salts thereof,

-mixtures thereof.

The term "salt" means salts of alkali metals of the acids such as Na, li or K, salts of monoethanolamine, diethanolamine or triethanolamine of the acids or basic amino acids such as lysine or arginine, and mixtures thereof.

Among the maleic anhydride copolymers and salts thereof, mention may in particular be made of the copolymers obtained by copolymerizing one or more maleic anhydride monomers and one or more monomers selected from the group consisting of vinyl acetate, vinyl alcohol, vinylpyrrolidone, olefins containing from 2 to 20 carbon atoms (e.g. octadecene, ethylene, isobutene, diisobutene, isooctenesAnd styrene) and mixtures thereof, said maleic anhydride comonomer being optionally partially or totally hydrolyzed, and more particularly copolymers of maleic anhydride and diisobutylene and salts thereof, and more particularly copolymers obtained by copolymerization of comonomers of the type described by the company rondymia (Rhodia) under the name Orotan And (5) selling products.

According to a particular embodiment of the invention, the dispersant thus corresponds to the following formula (I):

wherein:

r1 represents a hydrogen atom, a methyl group or a group

*-C(O)O ^- /X ⁺ Or a group-C (O) O-R6, wherein R6 represents a linear or branched C ₁ -C ₅₀ Preferably C ₁ -C ₈ Preferably C ₁ -C ₄ An alkyl group, a hydroxyl group,

r2, R3 and R4, which may be the same or different, represent a hydrogen atom or a methyl group,

r5 represents phenyl or straight-chain or branched C ₁ -C ₅₀ Preferably C ₁ -C ₂₀ Alkyl, or a radical-C (O) O-R7, where R7 represents a linear or branched C ₁ -C ₅₀ Preferably C ₁ -C ₈ Preferably C ₁ -C ₄ An alkyl group, a hydroxyl group,

x represents an integer ranging from 1 to 100,

y represents an integer ranging from 0 to 100,

n represents an integer of 1 to 1000,

x, y, and n are selected such that the equation "n (x + y)" is greater than or equal to 20, and preferably greater than or equal to 50,

X ⁺ represents a cation selected in particular from the group consisting of sodium atoms, potassium atoms and ammonium groups, and is preferably an ammonium group.

According to a more specific embodiment, the dispersant thus corresponds to the following formula (I'):

wherein:

r1, R2, R3 and R4 represent a hydrogen atom or C ₁ -C ₆ Alkyl groups, in particular methyl groups,

r5 represents a straight or branched C ₁ -C ₅₀ Preferably C ₁ -C ₈ Preferably C ₁ -C ₄ Alkyl groups, in particular methyl groups,

x represents an integer ranging from 1 to 100,

y represents an integer ranging from 0 to 100,

n represents an integer of 1 to 1000,

x+ represents a cation selected from among sodium atom, potassium atom and ammonium group, and is preferably an ammonium group.

wherein:

r1 represents a group-C (O) O ^- /X ⁺ Or a group-C (O) O-R5, wherein R5 represents a linear or branched C ₁ -C ₅₀ Preferably C ₁ -C ₈ Preferably C ₁ -C ₄ Alkyl groups, in particular methyl groups,

r2, R3 and R4 represent a hydrogen atom or C ₁ -C ₆ Alkyl groups, in particular methyl groups,

x represents an integer ranging from 1 to 100,

y represents an integer ranging from 0 to 100,

n represents an integer of 1 to 1000,

Preferably, the composition according to the invention comprises at least one ionic polymeric dispersant selected from the group consisting of:

a salt of a copolymer of at least two or more monomers selected from the group comprising acrylic acid, methacrylic acid or esters thereof,

salts of styrene/maleic anhydride copolymers,

salts of methacrylic acid homopolymers,

-and mixtures thereof.

Examples which may be mentioned include the following ionic polymeric dispersants:

-ammonium salts of copolymers of at least two or more monomers selected from the group comprising acrylic acid, methacrylic acid or esters thereof having the following INCI names: ammonium acrylic copolymers, e.g. Synthran, by the company Thai polymers under the name SynthranDispex AA sold or from Basoff company>

Ammonium salts of styrene/maleic anhydride (50/50) copolymers, in particular 30% aqueous solutions, of the type SMA by AmershamIs sold in the form of a roll,

sodium salts of styrene/maleic anhydride copolymers, in particular 40% aqueous solutions, referred to by the company Acciaiera with the index SMAIs sold in the form of a roll,

homopolymers of sodium methacrylate having the following INCI name: sodium polymethacrylate, in particular 25% aqueous solution, is prepared from Van derBit Company (r.t. vanderbilt Company, inc.) with index numbersThe product is sold as 7-N,

-mixtures thereof.

More particularly, a polymer of sodium methacrylate having the following INCI name will be used: sodium polymethacrylate, in particular in 25% aqueous solution, is designated by the index number from Vanderbilt Company (R.T. Vanderbilt Company, inc.)7-N.

The composition according to the invention preferably comprises one or more ionic polymer dispersants in a total content of greater than or equal to 0.05% by weight and less than or equal to 3% by weight, in particular ranging from 0.1% to 2% by weight, more in particular ranging from 0.1% to 1.5% by weight, and even more in particular ranging from 0.1% to 1% by weight, relative to the total weight of the composition.

Aqueous phase

The composition according to the invention comprises an aqueous phase.

The term "aqueous phase" means a phase comprising water and also all water-soluble or water-miscible solvents and ingredients.

The aqueous phase may contain demineralised water or alternatively floral water, such as cornflower water and/or mineral water such as bitmap (Vittel) water, lucas (Lucas) water or skin conditioning spring (La Roche Posay) water and/or spring water.

According to a preferred embodiment, the aqueous phase is present in a content ranging from 70% to 95% by weight relative to the total weight of the composition, preferably in a content ranging from 80% to 90% by weight relative to the total weight of the composition.

According to a preferred embodiment, the water is present in a content ranging from 40% to 80% by weight with respect to the whole composition, preferably in a content ranging from 60% to 70% by weight with respect to the total weight of the composition.

Thickening agent

For the purposes of the present invention, the term "thickener" means any organic or inorganic compound capable of increasing the viscosity of the aqueous composition according to the invention.

The thickener according to the invention is preferably water-soluble.

For the purposes of the present invention, the term "water-soluble thickener" means any thickener which is completely soluble in molecular form or miscible in the liquid aqueous phase or which is soluble in colloidal form (for example in micellar form) in the liquid aqueous phase.

As thickeners that can be used in the composition according to the invention, mention may be made of:

e.g. SynthalenPolyacrylic acid of the type;

-a carbomer-type polyacrylic acid crosslinked with pentaerythritol allyl ether, sucrose allyl ether or propylene allyl ether;

copolymers of at least two monomers chosen from acrylic acid, methacrylic acid or esters thereof, particularly Carbopol Aqua, available from Lubo advanced materials Co., ltdA product for sale;

copolymers of acrylic acid and acrylamide, named by Hercules, incSold as its sodium salt;

-crosslinked polyacrylic acid/C10-C30 alkyl acrylate copolymer with the following INCI name: acrylic ester/C10-C30 alkyl acrylic ester cross-linked polymer sold under the trade name of Lu Bo Runner advanced materials Co., ltdOr Carbopol->Selling;

an acrylamide methylpropanesulfonic acid polymer partially neutralized and crosslinked with ammonia having the following INCI name: ammonium polyacryl dimethyl taurate, sold under the trade name Hostacerin by Clariant, corpIs sold in the form of a roll,

-or->Type->Acrylamide copolymer sold by Sibirch company (SEPPIC), and

-Polyoxyethylenated alkyl methacrylate copolymers (crosslinked or uncrosslinked) and mixtures thereof.

Other examples of thickening polymers that may be mentioned include:

proteins, for example of vegetable origin, such as wheat or soybean proteins; proteins of animal origin, such as keratin, for example keratin hydrolysates and sulphonic keratins;

-anionic, cationic, amphoteric or nonionic chitin or chitosan polymers;

cellulosic polymers such as hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, ethylhydroxyethyl cellulose and carboxymethyl cellulose, and also quaternized cellulose derivatives;

vinyl polymers, such as polyvinylpyrrolidone, copolymers of methyl vinyl ether and maleic anhydride, copolymers of vinyl acetate and crotonic acid, copolymers of vinylpyrrolidone and vinyl acetate; copolymers of vinylpyrrolidone and caprolactam; polyvinyl alcohol;

associative polychloroetsters, e.g. from Servo Delden CorpPolymer (named SER AD->Sold, this molecule carries urethane functions and has a weight average molecular weight of 1300), OE is an oxyethylene unit, rheolate with urea functions +. >Sold by the company Viiles (Rheox), or Rheolate +.>Or (b)(these polymers are sold in pure form) or DW ++from Rogowski company>With C ₂₀ Alkyl chains and urethane linkages are sold as 20% solids in water. Solutions or dispersions of these associative polychloroetsters, especially in water or in aqueous alcoholic media, can also be used. Examples of such polymers which may be mentioned include SER AD FX1010, SER AD +.>And SER AD->Rheolate sold by the company Vigress +.>Rheolate/>And Rheolate->Product DW from romnet hasi can also be usedAnd DW->And also Acrysol RM +.>Or Acrysol->Or alternatively Borchigel LW from Borches (Borches)>

-optionally modified polymers of natural origin, such as:

-acacia, guar gum, xanthan gum derivatives, karaya gum;

-alginate and carrageenan;

-glycosaminoglycans, hyaluronic acid and derivatives thereof;

shellac resin, shanda gum, dammar resin, elemene and copal resin;

-deoxyribonucleic acid;

mucopolysaccharides, such as hyaluronic acid and chondroitin sulfate,

and mixtures thereof.

More particularly, a thickener selected from the following will be used:

at least two copolymers of the type INCI named acrylic, methyl Copolymers of monomers of acrylic acid or esters thereof, in particular Carbopol Aqua, available from Lubo advanced materials Co., ltdA product for sale;

polyacrylic acid/C10-C30 alkyl acrylate crosslinked copolymer with the following INCI name: acrylic acid ester/C10-C30 alkyl acrylic acid ester crosslinked polymers, e.g. from Lubo advanced materials Co., ltd under the trade names Pemulen TR1 and PemulenOr Carbopol->Carbopol ETD2020/>Carbopol1342Carbopol SC/>Carbopol SC 500/>Carbopol Ultrez 20Carbopol Ultrez 21/>A product for sale;

-and mixtures thereof.

The thickener may preferably be used in a proportion of 0.05 to 3% by weight solids relative to the total weight of the aqueous phase, in particular in a proportion of 0.1 to 2% by weight relative to the total weight of the composition.

Particulate dye

The particulate dye is particularly intended to impart a coloured appearance or pearlizing effect to the composition useful for making up the skin.

The particulate dye is preferably selected from pigments and nacres and mixtures thereof.

This dye is preferably present in a content ranging from 5% to 40% by weight and more particularly from 10% to 30% by weight, relative to the total weight of the composition. According to a preferred mode of the invention, the dye is present in the composition in a total content ranging from 15% to 25% by weight relative to the total weight of the composition.

Pigment

The term "pigment" is understood to mean any shaped mineral or organic particles, white or coloured, which are insoluble in the medium of the composition and are intended to colour the composition.

These pigments may be white or coloured, as well as mineral and/or organic.

The term "mineral pigment" means any pigment satisfying the definition in the section on inorganic pigments in Ullmann's encyclopedia. Among the mineral pigments which can be used in the present invention, mention may be made of zirconia or ceria, and also zinc oxide, iron oxides (black, yellow, or red) or chromium oxide, manganese violet, ultramarine blue, chromium hydroxide, and ferric blue, titanium dioxide, and metal powders (e.g., aluminum powders or copper powders). The following mineral pigments may also be used: ta ₂ O ₅ 、Ti ₃ O ₅ 、Ti ₂ O ₃ TiO, tiO and TiO ₂ ZrO in the form of a mixture of (a) ₂ 、ZrO ₂ 、Nb ₂ O ₅ 、CeO ₂ 、ZnS。

The term "organic pigment" means any organic compound that is insoluble in the medium of the composition and is intended to color the composition.

The organic pigment may be selected from the following materials, and mixtures thereof:

-cochineal (cochineal) is present,

organic pigments of azo dyes, anthraquinone dyes, indigo dyes, xanthene dyes, pyrene dyes, quinoline dyes, triphenylmethane dyes or fluoran dyes.

Among the organic pigments, mention may be made in particular of D & C certified pigments known by the following names: d & C blue No. 4, D & C brown No. 1, D & C green No. 5, D & C green No. 6, D & C orange No. 4, D & C orange No. 5, D & C orange No. 10, D & C orange No. 11, D & C red No. 6, D & C red No. 7, D & C red No. 17, D & C red No. 21, D & C red No. 22, D & C red No. 27, D & C red No. 28, D & C red No. 30, D & C red No. 31, D & C red No. 33, D & C red No. 34, D & C red No. 36, D & C violet No. 2, D & C yellow No. 7, D & C yellow No. 8, D & C yellow No. 10, D & C yellow No. 11, FD & C blue No. 1, FD & C green No. 3, FD & C red No. 40, FD & C yellow No. 5, FD & C yellow No. 6.

Chemical materials corresponding to each of The previously mentioned organic dyes are mentioned in The publication "International Cosmetic Ingredient Dictionary and Handbook [ International Cosmetic composition dictionary and handbook ]",1997 edition, pages 371 to 386 and 524 to 528 of The Cosmetic, cosmetic and fragrance Association ], toiletry and Fragrance Association, the contents of which are incorporated by reference into The present patent application.

Depending on the particular mode, the pigment or pigments used may be surface treated and may be coated with, inter alia, at least one hydrophilic compound.

For the purposes of the present invention, "coating" of the pigments according to the invention generally means the surface treatment of the pigments with a surface-agent which absorbs, adsorbs or grafts onto the pigments in whole or in part.

The surface-treated pigments may be prepared according to surface-treatment techniques of a chemical, electrical, mechanochemical or mechanical nature, which are known to the person skilled in the art. Commercial products may also be used.

The surfactant may be absorbed, adsorbed or grafted onto the pigment by evaporation of the solvent, chemical reaction, and covalent bond formation.

According to one variant, the surface treatment consists of the coating of pigments.

The coating may comprise 0.1 to 20% by weight and in particular 0.5 to 10% by weight, relative to the total weight of the coating pigment.

Coating may be achieved, for example, by: the liquid surfactant is adsorbed onto the surface of the solid particles by simply mixing the particles with the surfactant under agitation, optionally with heating, prior to incorporation of the particles into the other ingredients of the cosmetic or care composition.

Coating may be accomplished, for example, by chemically reacting the surfactant with the surface of the solid pigment particles and forming covalent bonds between the surfactant and the particles. This method is described in particular in patent US 4,578,266.

Chemical surface treatment may include diluting the surfactant in a volatile solvent, dispersing the pigment in this mixture, and then slowly evaporating the volatile solvent so that the surfactant is deposited at the surface of the pigment.

The surface treatment agent may be hydrophilic, such as those described, for example, in Cosmetics & Cosmetics [ Cosmetics & Toiletries ], month 2 1990, volume 105, pages 53-64. Mention may be made, for example, of amino acids, C1-C5 alkanolamines, silica, sodium hexametaphosphate or glycerol or mixtures thereof, PEG-12 polydimethylsiloxane, sodium glycerophosphate, PEG-7 glycerolcocoate+methylsilanol tri-PEG-8 glycerolcocoate+polyquaternium-7, chitosan, methoxy PEG-10 propyltrimethoxysilane, PEG/PPG-18/18 polydimethylsiloxane, microcrystalline cellulose and polyethylene glycol alkoxysilane.

The composition according to the invention may comprise pigments in a content ranging from 0% to 30% by weight relative to the total weight of the composition, preferably ranging from 0% to 20% by weight and preferably ranging from 1% to 15% by weight relative to the total weight of the composition. According to a preferred mode of the invention, the pigment is present in the composition in a content ranging from 1% to 10% by weight relative to the total weight of the composition.

Mother-of-pearl

The term "mother-of-pearl" is understood to mean any form of coloured particles (which may or may not be iridescent), in particular produced by a certain mollusk within its shell, or alternatively synthesized, and which have a colouring effect via optical interference.

Examples of nacres that may be mentioned include pearlescent pigments such as titanium mica coated with iron oxide, mica coated with bismuth oxychloride, titanium mica coated with chromium oxide, in particular titanium mica coated with an organic dye, and also pearlescent pigments based on bismuth oxychloride.

They may also be mica particles, on the surface of which at least two sequential layers of metal oxide and/or organic dye are superimposed.

These particles may be chosen from particles comprising a natural or synthetic substrate at least partially coated with at least one layer of at least one metal oxide chosen, for example, from titanium oxide (in particular TiO ₂ ) Iron oxide (especially Fe ₂ O ₃ ) Tin oxide, chromium oxide, barium sulfate and the following materials: mgF (MgF) ₂ 、CrF ₃ 、ZnS、ZnSe、SiO ₂ 、Al ₂ O ₃ 、MgO、Y ₂ O ₃ 、SeO ₃ 、SiO、HfO ₂ 、ZrO ₂ 、CeO ₂ 、Nb ₂ O ₅ 、Ta ₂ O ₅ 、M _o S ₂ And mixtures or alloys thereof.

Examples of such particles that may be mentioned include particles comprising synthetic mica substrates coated with titanium dioxide, or glass particles, in particular calcium borosilicate particles, coated with brown iron oxide, titanium oxide, tin oxide or mixtures thereof, for example as commercially available from Engelhard corporation (Engelhard) Label nameAnd (5) selling products.

The mother-of-pearl may have a yellow, pink, red, bronze, orange, brown, gold, and/or copper hue.

Non-limiting examples of mother-of-pearl that may be specifically mentioned, alone or as a mixture, include mother-of-pearl comprising the following elements:

mica-titanium oxide (e.g., timica spark le, commercially available from Basf Corp.)Flamenco +.>Candurin Brown from Merck company>Pearlescent Pigment Prestige +.>Sell);

mica-titanium oxide coated with N-lauroyl-L-lysine (e.g., commercially available from Dadong chemical industry Co., ltd., reference number LLD-10 Flamingco)Sell);

mica-iron oxide (e.g. as per commercial index Pearlescent Pigment Prestige Soft from the company Sudama)Colorona Bronze from Merck>Timica Golden from Basoff company>Candurin Light from merck corporation>Duocromie YR 422 +.>Gemtone Tan Opal G>Sell);

mica-titanium oxide-iron oxide (e.g., as described in commercial index Timica Brilliant Gold, 212, G Gemtone Goldstone from basf) Or Timica Golden->Sell);

mica-bismuth oxychloride-iron oxide (e.g., chroma-Lite with commercial index from basf corporation)Sell);

mica-titanium oxide-chromium oxide-iron oxide (e.g., gemtone, commercially available from Basf Corp., ltd.)Sell);

mica-titanium oxide-tin oxide (e.g., as per commercial index Flamenco Super Blue 630 from basf)Helios ++Helios from Topy industries Co., ltd>Sell);

mica-silica-titania (e.g., timiron Splendid, commercial index from Merck Corp.)Sell);

sodium calcium borosilicate tablets coated with titanium oxide and tin oxide (e.g., as described in commercial index Reflecks Rays of Red from basf corporationSell);

sodium calcium borosilicate sheet coated with tin oxide and iron oxide (e.g., mirage spark ling, commercial index number from Aika Co., ltd. (Eckar))Sell);

aluminum calcium borosilicate sheet coated with titanium oxide and tin oxide, optionally treated with silica (e.g., with commercial index numbers from merck corporationSell);

aluminum calcium borosilicate sheet coated with silica and tin oxide (e.g., golden Jetel, commercial index number from merck Corp.) Sell);

glass powder coated with titanium oxide (e.g. under commercial index Reflecks Dimensions Glittering Gold from basf)Or metazine from Nitro Board Co (NSG)Sell);

alumina and titania (e.g., as per commercial index Spectraflex Focus Red from Sun Corp (Sun)Sell);

bronze powder (e.g., with commercial index number Visionaire Bright Sunflower from ai card company)Sell);

synthetic fluorophlogopite and magnesium silicate and titanium dioxide and tin oxide (e.g., under commercial index number Sunshine Daybreak from solar chemical company)Sell).

For the purposes of the present invention, the term "mica" includes natural mica and synthetic mica.

According to a particularly preferred mode, the particulate dye will be selected from titanium dioxide particles, iron oxide particles and mixtures thereof.

According to a particularly preferred form of the invention, the composition for making up and/or caring for keratin materials, such as the skin, comprises, in particular in the form of an aqueous particle dispersion, comprising a physiologically acceptable medium, in particular for coating the keratin materials, and more particularly:

a) An aqueous phase; and

b) At least one matte effect filler selected from the group consisting of boron nitride, polymethylsilsesquioxane powder, and mixtures thereof;

c) At least one aqueous dispersion of an amino methyl propanoate salt of a copolymer of allyl methacrylate having the following INCI name with one or more monomers selected from acrylic acid, methacrylic acid or esters thereof, as solid particles formed of film-forming polymer suspended in an aqueous phase: acrylic acid ester/methacrylic acid allyl ester copolymer AMP salt; and

d) At least one ionic polymer dispersant selected from sodium methacrylate homopolymers;

e) At least one thickener selected from the group consisting of:

-a copolymer of at least two monomers selected from acrylic acid, methacrylic acid or esters thereof;

polyacrylic acid/acrylic acid C ₁₀ -C ₃₀ Alkyl ester crosslinked copolymers;

an acrylamide methylpropanesulfonic acid polymer partially neutralized and crosslinked with ammonia; and mixtures thereof, and

f) At least one particulate dye selected from titanium dioxide, iron oxide and mixtures thereof.

Additive agent

The composition according to the invention may also comprise further cosmetic ingredients conventionally used in aqueous cosmetic compositions, in particular for making up and/or caring for the skin. Examples which may be mentioned in particular include additives selected from the group consisting of polyols, monohydric alcohols, water-soluble dyes, preservatives, antioxidants, chelating agents, sequestering agents, defoamers, fragrances, sunscreens, bactericides, water-soluble active agents and mixtures thereof.

Needless to say, the person skilled in the art will take care to choose the optional further ingredients and/or the amounts thereof such that the advantageous properties of the composition according to the invention are not or not substantially adversely affected by the envisaged addition.

More particularly, the composition according to the invention contains at least one additive selected from polyols, monohydric alcohols and mixtures thereof.

Polyhydric alcohol

The composition may also comprise a polyol miscible with water at room temperature (25 ℃), in particular selected from polyols containing from 2 to 20 carbon atoms, preferably from 2 to 10 carbon atoms and preferably from 2 to 8 carbon atoms, such as glycerol, propylene glycol, 1, 3-butanediol, pentanediol, hexanediol, octanediol, dipropylene glycol, or diethylene glycol; glycol ethers (especially containing 3 to 16 carbon atoms), such as monopropylene glycol, dipropylene glycol, or tripropylene glycol (C) ₁ -C ₄ ) Alkyl ethers, monoethylene glycol, diethylene glycol, or triethylene glycolAlcohols (C) ₁ -C ₄ ) Alkyl ethers; polyethylene glycol; and mixtures thereof.

More preferably propylene glycol will be used.

According to a preferred mode of the invention, the polyol is preferably present in a content ranging from 1% to 20% by weight relative to the total weight of the composition and more particularly ranging from 5% to 15% by weight relative to the total weight of the composition.

Monohydric alcohols

Furthermore, the composition according to the invention may comprise a monohydric alcohol containing 2 to 5 carbon atoms, such as ethanol or isopropanol.

Ethanol will be more preferably used.

According to a preferred mode of the invention, the monohydric alcohol is present in a content ranging from 1% to 10% by weight relative to the total weight of the composition and preferably in a content ranging from 3% to 7% by weight relative to the total weight of the composition.

Additional dyes

According to a particularly preferred mode of the invention, the composition further comprises at least one water-soluble dye.

For the purposes of the present invention, the term "water-soluble dye" means any natural or synthetic, generally organic, compound which is soluble in the aqueous phase or in a water-miscible solvent and is capable of being coloured.

As water-soluble dyes suitable for use in the present invention, mention may be made in particular of synthetic or natural water-soluble dyes, such as FDC red 4, DC red 6, DC red 22, DC red 28, DC red 30, DC red 33, DC orange 4, DC yellow 5, DC yellow 6, DC yellow 8, FDC green 3, DC green 5, FDC blue 1, betanin (betanin), carmine, copper chlorophyllin, methylene blue, anthocyanin (desglucocyanin), black carrot, hibiscus, elder (elder)), caramel pigment (caramel) and riboflavin.

Cosmetic application

According to one embodiment, the composition of the invention may advantageously be in the form of a composition for caring for the body or the face, in particular the skin of the face.

According to another embodiment, the composition of the invention may advantageously be in the form of a composition for making up the body or the face, in particular the skin of the face.

The composition of the invention may advantageously be in the form of a foundation.

According to another mode of this embodiment, the composition of the invention may advantageously be in the form of an eye shadow or a face powder.

Such compositions are prepared, inter alia, according to the general knowledge of the person skilled in the art.

Cosmetic box

According to another aspect, the invention also relates to a cosmetic assembly comprising:

i) A container defining at least one compartment, the container being closed by a closure member; and

ii) a composition as described before placed inside said compartment.

The container may be in any suitable form. It may be in particular in the form of a bottle, tube, can, box, spray can (can), pouch or box.

The closure member may be in the form of a removable plug, cap, lid, tear strip or capsule, in particular of the type comprising a body attached to the container and a cover hinged to the body. It may also be in the form of a member for selectively closing the container, in particular a pump, valve or flap valve.

The container may be combined with an applicator. The applicator may be in the form of a fine brush, as described for example in patent FR 2 722 380. The applicator may be in the form of a foam or elastomer pad, felt-tipped pen, or spatula. The applicator may be free (a puff or sponge) or securely fastened to a rod carried by the closure member, as described for example in patent US 5 492 426. The applicator may be firmly attached to the container as described for example in patent FR 2 761 959.

The product may be contained directly or indirectly in the container. For example, the product may be arranged on an impregnated carrier (in particular in the form of a wipe or pad), arranged (individually or in multiple) in a box or pouch. Such a carrier for incorporation into a product is described, for example, in patent application WO 01/03538.

The closure member may be coupled to the container by a screw engagement. Alternatively, the coupling between the closure member and the container is not by screw engagement, in particular via a bayonet mechanism, but by clamping-fastening (click-fastening), clamping, welding, adhesive bonding or by magnetic attraction. The term "grip-fastening" is understood to mean in particular any system involving elastic deformation of a portion, in particular of a closure member, beyond the edge or bead (bead) of material, and then returning to the elastic unstressed position of said portion after the edge or bead has been exceeded.

The container may be at least partially made of a thermoplastic material. Examples of thermoplastic materials that may be mentioned include polypropylene and polyethylene.

Throughout the specification (including the claims) the term "comprising" is to be understood as synonymous with "including at least one" unless otherwise indicated.

The expressions "between" and "ranges from" to "are understood to mean including the limit values unless otherwise indicated.

The invention is illustrated in more detail by means of the examples presented below and the accompanying drawings. Unless otherwise indicated, the indicated amounts are expressed in weight percent.

Examples

Example 1: foundation in the form of an aqueous particle dispersion

The procedure is as follows:

the composition was manufactured at room temperature (25 ℃) in the following manner.

Phase A1 was prepared by: the two thickening polymers were introduced into the water in the tank with stirring at 4000rpm for 15 minutes using a paddle mixer, and then triethanolamine was added with stirring at the same speed for 5 minutes. Propylene glycol and sodium polymethacrylate were continuously added with stirring at the same speed for 5 minutes, and then the pigment and synthetic mica were added at the same speed. After one minute, the wall was scraped off and turbine mixing was performed at the same speed for 20 minutes. Phase A2 was prepared by: the various ingredients were introduced into water and added to the tank containing phase A1. Phase B and phase C were then added successively to the resulting mixture with stirring at the same speed for 20 minutes.

An aqueous dispersion in which the pigment was uniformly dispersed was obtained.

Test of matte effect and matte effect durability

Principle of measurement

The gloss of the skin was measured using a Samba fdt_fr2 polarization camera, which is a black and white polarization imaging system, with which images were acquired with parallel (P) and cross (C) polarized light. By analyzing the image obtained by subtracting (P-C) the two images, the gloss is quantified by measuring the average gray level of the brightest 5% pixel corresponding to the gloss area.

Test program

The test was performed as follows:

the test was performed in vivo in 17 caucasian individuals 18 to 65 years old, who had oily, light to medium wrinkled skin, pale complexion, and smooth skin (no wrinkles or redness on the cheeks). Each volunteer received two products for half-face testing. This test was performed in parallel groups and individuals were randomly assigned to treatment groups.

15 minutes before the start of the test, the participants arrived at the conditioned waiting room (22 ℃ ±2 ℃). They remove makeup and take an image of one of their cheeks with a polarized camera. This image allows measurement of gloss at T0 prior to application of the cosmetic.

Next, 100mg of foundation was weighed out on a petri dish and applied with a bare finger to the half face where the measurement under T0 was performed.

After a drying time of 15 minutes, an image of the cosmetic cheek was taken with a polarized camera. This image allows to measure the gloss immediately after the application of the cosmetic (Timm).

The model was then returned to the conditioned room for 3 hours.

Finally, images of the cosmetic cheeks after a waiting time of 3 hours were taken with a polarized camera. This image allows to measure the gloss after 3 hours of makeup (T3 h).

Representing the result

The difference deltae (Timm-T0) that measures the effect of the cosmetic on the skin is calculated. Negative values mean that the cosmetic reduces the gloss of the skin and therefore it has a matte effect.

The difference DeltaE (T3 h-Timm) that measures the persistence of this effect is then calculated. The values obtained should be as low as possible, which means that the cosmetic effect does not change over time.

The results obtained are shown in the following table.

The compositions according to the invention have a good matte effect and a good permanence of this effect after 3 hours.

Testing of colour and matte effect permanence

Principle of measurement

Using skin image acquisition means, e.g. as described in patent EP1288706The coloration of the skin is measured mechanically and according to the methods indicated in said document.

Test program

The test was performed as follows:

15 minutes before the start of the test, the participants arrived at the conditioned waiting room (22 ℃ ±2 ℃). They remove makeup and useThe machine evaluates the color of one of their cheeks at T0 prior to makeup.

After a drying time of 15 minutes, the immediate coloration of the cheeks (Timm) after application is measured.

The model was then returned to the conditioned room for 3 hours.

After a waiting period of 3 hours, useThe machine measures the immediate coloration of the skin after application of the cosmetic to the cheek.

This image allows to measure the coloration of the cheeks made up after 3 hours of make-up (T3 h).

Representing the result

The difference deltae (Timm-T0) that measures the effect of the cosmetic on the skin is calculated.

The difference deltae (T3 h-Timm) that measures the permanence of this color effect is then calculated. The values obtained should be as low as possible, which means that the color effect does not change over time.

The results obtained are shown in the following table.

The composition according to the invention has a good colouring effect and a good permanence of this effect after 3 hours.

Comparative sensory test of transfer resistance

The transfer resistance effect of the composition of example 1 in the form of an aqueous coloured particulate dispersion according to the invention was compared with the transfer resistance effect of two reference products of water-based foundations in the form of water-in-oil emulsions on the market, namely:

1) Product WATER BLEND FACE&BODY(i.e., mintel product number 4792105), the list of ingredients is:

water, CI 77891, hydrogenated polyisobutene, sorbitan trioleate, pentaerythritol tetraisostearate, methylpropanediol, glycerol, perfume, mango seed oil, butylene glycol, phenoxyethanol, glyceryl octoate, tromethamine, CI 77492, acrylic acid (esters) of C10-30 alkanol acrylate cross-linked polymers, 1, 2-pentanediol, panthenol, aluminium dimyristate, CI 77491, CI 77499, butylated hydroxytoluene, tocopherol (vitamin E);

2) Product LIQUID AIR TOO COOL FOR SCHOOL ART in the form of a water-in-oil emulsion(i.e., mintel product number 4891985), the list of ingredients is:

water, phenyl trimethicone, denatured alcohol, dimethicone, isododecane, ethylhexyl methoxycinnamate, silica, butylene glycol, PEG-10 dimethicone, titanium dioxide, methyl methacrylate cross-linked polymer, polymethylsilsesquioxane, mica, sodium chloride, polydimethylsiloxane/PEG-10/15 cross-linked polymer, isohexadecane, squalane, potassium sorbate, sodium dehydroacetate, disodium stearoyl glutamate, tocopheryl acetate, perfume, titanium isopropoxide triisostearate, maltodextrin, moringa seed extract, xylitol glucoside, aluminum hydroxide, anhydroxylitol, xylitol, dipropylene glycol, citronellol, benzyl benzoate, butylphenyl methylpropionaldehyde, linalool, sodium citrate, alpha-isopropyl ionone, coumarin, tocopherol, titanium dioxide, yellow iron oxide, red iron oxide, black iron oxide.

A group of 14 women with normal skin were subjected to sensory testing. Each evaluator (skilled in mastering foundations) was trained by the reference foundation expert with respect to the score attributed to the reference product for the transfer resistance standard. Participants are foundation users who show great interest in cosmetic products. Their memory, accuracy, mathematical logic, concentration and motivation enable them to meet the conditions to gain entry into the participant's state at the end of the training session. The regimen used was an in vivo regimen that was as close as possible to the pose used by the consumer, thus representing a natural pose for personal application of the foundation formulation. The transfer resistance criteria were evaluated on a scale of 0 to 5. The higher the value, the greater the transition.

The results obtained are shown in the following table as the average of the scores obtained:

composition 1 in the form of an aqueous coloured particulate dispersion according to the invention gives a significantly better transfer resistance than the reference aqueous formulation of foundations in the form of a water-in-oil emulsion on the market.

Claims

1. A composition in the form of an aqueous particle dispersion, the composition comprising:

a) An aqueous phase; and

b) At least one matte effect filler selected from silica powders; polytetrafluoroethylene powder; silicone resin powder, acrylic copolymer powder; hollow hemispherical silicone particles; hydrophobic silica aerogel particles; a crosslinked elastomeric organopolysiloxane powder; crosslinked bullet coated with silicone resin Sex organopolysiloxane powder; polyamide powder; starch powder; talc/TiO ₂ Alumina/silica composite powder; silica/TiO ₂ A composite material; spherical cellulose particles; clay; perlite; boron nitride and mixtures thereof; and

c) Solid particles formed from at least one film-forming polymer suspended in the aqueous phase, the film-forming polymer being an aqueous dispersion of an amino methylpropanoxide of a copolymer of allyl methacrylate with one or more monomers selected from acrylic acid, methacrylic acid or esters thereof, having the following INCI names: acrylic acid ester/methacrylic acid allyl ester copolymer AMP salt; and

d) At least one ionic polymeric dispersant selected from the group consisting of:

- (meth) acrylic acid homopolymers and salts thereof; and

e) At least one thickener selected from the group consisting of:

polyacrylic acid/C10-C30 alkyl acrylate crosslinked copolymer with the following INCI name: acrylic ester/C10-C30 alkyl acrylic ester cross-linked polymer;

an acrylamide methylpropanesulfonic acid polymer partially neutralized and crosslinked with ammonia having the following INCI name: ammonium polyacryl dimethyl taurate;

-and mixtures thereof; and

f) At least one particulate dye selected from the group consisting of pigments and nacres and mixtures thereof.

2. The composition of claim 1, wherein the matte effect filler is present at a concentration ranging from 0.1 wt% to 5 wt% relative to the total weight of the composition.

3. Composition according to claim 1 or 2, wherein the filler is selected from the group comprising:

-a silica powder;

-polymethylsilsesquioxane powder;

-poly (methyl (meth) acrylate) (PMMA) powder;

-perlite;

-boron nitride;

-and mixtures thereof.

4. The composition of claim 1, wherein the film-forming polymer is present at a solids content ranging from 0.1 wt% to 5 wt%, relative to the total weight of the composition.

5. The composition of claim 1, comprising an ionic polymer dispersant in a total content of greater than or equal to 0.05 wt% and less than or equal to 3 wt% relative to the total weight of the composition.

6. The composition of claim 1, wherein the thickener is present in a proportion of 0.05 to 3 wt% solids relative to the total weight of the aqueous phase.

7. The composition of claim 1, wherein the particulate dye is present in an amount ranging from 5 wt% to 40 wt% relative to the total weight of the composition.

8. The composition of claim 1, wherein the particulate dye is selected from the group consisting of titanium dioxide particles, iron oxide particles, and mixtures thereof.

9. The composition of claim 1, wherein the aqueous phase is present in an amount ranging from 70 wt% to 95 wt% relative to the total weight of the composition.

10. The composition of claim 1, wherein the water is present in an amount ranging from 40 wt% to 80 wt% relative to the total weight of the composition.

11. The composition of claim 1, comprising at least one additive selected from the group consisting of polyols, monohydric alcohols, and mixtures thereof.

12. The composition of claim 1 in the form of a foundation.

13. The composition of claim 1 in the form of an eye shadow or face powder.

14. A process for coating keratin materials, characterized in that it comprises the application to the keratin materials of a composition as defined according to any one of the preceding claims.